Detergent compositions containing cellulase enzyme and selected perfumes for improved odor and stability

ABSTRACT

A detergent composition containing cellulase and perfume is provided. Specifically, the detergent composition comprises: (a) a cellulase enzyme; and (b) a perfume containing at least 25% by weight of at least one fragrance material selected from the group consisting of aliphatic ketones with a molecular weight of between 200 and 350 AMU, aromatic ketones with a molecular weight of between 150 and 350 AMU, aliphatic aldehydes with a molecular weight of between 160 and 350 AMU, aromatic aldehydes with a molecular weight of between 150 and 350 AMU, condensation products of aldehydes and amines with a molecular weight between 190 and 350 AMU, aromatic and aliphatic lactones with a molecular weight between 140 and 350 AMU, aromatic and aliphatic ethers with a molecular weight between 150 and 350 AMU, aliphatic alcohols with a molecular weight between 200 and 350 AMU, aromatic and aliphatic esters with a molecular weight between 190 and 350 AMU and mixtures thereof. The perfume is substantially free of halogenated fragrance materials and nitromusks.

FIELD OF THE INVENTION

The present invention generally relates to detergent compositionscontaining celluase enzyme and selected perfumes. More particularly, theinvention relates to detergent compositions incorporating perfumes whichcounteract the residual malodors associated with cellulase enzyme, thefeedstock in which cellulases are contained, and cellulase treatedlaundry. Also, the perfumes selected herein exhibit improvedcompatibility with the cellulase enzyme contained in the detergentcomposition. The detergent composition of the invention may beformulated as a liquid, granular, or laundry bar composition.

BACKGROUND OF THE INVENTION

In the art of detergency, formulators have used enzymes in detergentcompositions for a variety of fabric laundering purposes, includingremoval of protein-based, carbohydrate-based, or triglyceride-basedstains, and for the prevention of refugee dye transfer, and for fabricrestoration. Typically, enzymes such as protease, amylases, lipases,cellulases and peroxidases have been used for such purposes. One majordrawback to the use of enzymes in detergents is the unpleasant odorcontribution such enzymes and the feedstocks in which the enzymes areusually contained and delivered. These enzymes and their feedstocks arecomplex mixtures obtained from fermentation processes and they typicallycontain many offensive odor contaminants which ultimately find their wayinto the detergent products in which the enzymes are included. Theresulting malodors in such detergent compositions does not appeal toconsumers. Additionally, the detergency enzymes have a tendency to leaveresidual odors on the fabric itself which leads to consumerdissatisfaction, as well.

In the past, these drawbacks have often been countered by limiting thelevel of enzyme used in the composition. However, this approachrestricts product efficacy and does not entirely eliminate the malodorproblem. Another approach entails "purifying" the enzyme so as to reducethe amount of malodor constituents in the enzyme itself prior toincorporation into the detergent. More particularly, detergentcompositions containing protease enzyme have been purified such thatthey do not have a detectable odor in distilled water at specifiedconcentration levels. While this approach provides a viable option, itrequires an additional step in the manufacture of the detergent (i.e.the purifying step), thereby resulting in a more expensive product.

Other attempts in the art have also only focused on especiallyproblematic enzymes. By way of example, there have been attemptsdirected to counteracting malodors associated with fabrics launderedwith detergent compositions containing lipases. Enzymes such as lipasesand protease have been known to exhibit offensive odors as contained inthe detergent as well as to cause residual malodors on fabrics launderedwith such protease or lipase-containing detergents. In that regard,certain perfumes have been used to mask the residual odors on fabricscaused by the lipase-containing detergents.

As is known, cellulase enzymes have been used in the art of detergencyfor purposes of providing fabric care as well as cleaning performance.It has also been known that perfumes may be included incellulase-containing detergents. However, there is still a need for adetergent composition containing specific perfumes especially suitablefor counteracting malodors associated with cellulase enzyme and itsfeedstock as well as the residual malodors which may be found on fabricslaundered with such cellulase-containing detergents. Moreover, it wouldbe desirable to have a means by which the compatibility of the cellulaseenzyme and perfume can be improved so as to provide a more stabledetergent.

Accordingly, there remains a need for a cellulase-containing detergentcomposition which does not itself exhibit malodors or cause fabricslaundered such a composition to have residual malodors. There is also aneed in the art for such a cellulase-containing detergent compositionwhich exhibits improved stability.

BACKGROUND ART

The following references disclose proteases and lipases in detergents:Moeddel, U.S. Pat. No. 4,515,705 (Procter & Gamble); Behan et al, EP430, 315 (Unilever); and, Watanabe et al, JP-A-63-334931 (Lion Co.). Thefollowing references disclose cellulase enzymes and their use indetergent compositions: Barbesgaard et al, U.S. Pat. No. 4,435,307 (NOVOIndustries A/S); GB-A-2,075,028; GB-A-2,095,275; and GB-A-1,368,599.

SUMMARY OF THE INVENTION

The present invention meets the needs identified above by providing acellulase-containing detergent composition which does not emit malodorsthat are offensive to consumers and which exhibits improved productstability. The cellulase-containing detergent composition achieves thisby incorporating selected perfume formulations into the detergent whichsurprisingly reduce the odor problem associated with cellulase enzymesand their feedstock. Further, the selected perfume formulations used inthe instant detergent composition are less interactive with cellulaseenzymes and thus cause the overall stability of the detergentcomposition to be surprisingly improved. The cellulase enzymes containedin the detergent composition of the invention can be both bacterial andfungal cellulase, although fungal cellulases are preferred. Numerousperfume formulations suitable for use in the detergent of the inventioncan be prepared from known perfume or fragrance ingredients.

As used herein, the designation "AMU" refers to atomic weight and mayalso be expressed as g/mole. All percentages, ratios and proportionsused herein are by weight, unless otherwise specified. All documentsincluding patents and publications cited herein are incorporated hereinby reference.

In accordance with one aspect of the invention, a detergent compositioncontaining cellulase and perfume is provided. Specifically, thedetergent composition comprises: (a) a cellulase enzyme; and (b) aperfume containing at least 25% by weight of at least one fragrancematerial selected from the group consisting of aliphatic ketones with amolecular weight of between 200 and 350 AMU, aromatic ketones with amolecular weight of between 150 and 350 AMU, aliphatic aldehydes with amolecular weight of between 160 and 350 AMU, aromatic aldehydes with amolecular weight of between 150 and 350 AMU, condensation products ofaldehydes and amines with a molecular weight between 190 and 350 AMU,aromatic and aliphatic lactones with a molecular weight between 140 and350 AMU, aromatic and aliphatic ethers with a molecular weight between150 and 350 AMU, aliphatic alcohols with a molecular weight between 200and 350 AMU, aromatic and aliphatic esters with a molecular weightbetween 190 and 350 AMU and mixtures thereof. The perfume preferably issubstantially free of halogenated fragrance materials and nitromusks.The detergent composition surprisingly exhibits decreased malodors ascompared with other cellulase-containing detergents which do not includeperfume formulations as defined herein.

In another embodiment of the invention, a method of laundering soiledfabrics is provided. The method comprises the step of contacting thesoiled fabrics with an aqueous medium containing an effective amount ofa detergent composition as described herein. Yet another embodiment ofthe invention is directed to a laundry bar composition suitable forhandwashing soiled fabrics. Other aspects of the invention includegranular as well as liquid forms of the detergent composition describedherein.

Accordingly, it is an object of the invention to provide a detergentcomposition containing cellulase enzyme which does not have the malodorproblem normally associated with cellulase-containing detergents. It isalso an object of the invention to provide such a cellulase-containingdetergent which has improved stability as a result of improvedcompatibility of celluase enzyme and the perfume in the detergent. Theseand other objects, features and attendant advantages of the presentinvention will become apparent to those skilled in the art from areading of the following detailed description of the preferredembodiment and the appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In its broadest aspect, the present invention is directed to a detergentcomposition containing a cellulase enzyme and a perfume as definedherein, together which provide a detergent having improved odor andstability. The perfumes suitable for use in the detergent compositioncan be formulated from known fragrance ingredients and preferablycontain at least 25%, preferably from about 25% to about 40%, and mostpreferably from about 40% to about 60%, by weight of at least onefragrance material selected from several categories of perfumeingredients. For purposes of enhancing environmental compatibility, theperfume is substantially free of halogenated fragrance materials andnitromusks.

Cellulase Enzyme

The cellulase enzymes used in the instant detergent composition arepreferably incorporated at levels sufficient to provide up to about 5 mgby weight, more preferably about 0.01 mg to about 3 mg, of active enzymeper gram of the composition. Stated otherwise, the compositions hereinpreferably comprise from about 0.001% to about 5%, preferably 0.01%-1%by weight of a commercial enzyme preparation.

The cellulase suitable for the present invention include both bacterialor fungal cellulase. Preferably, they will have a pH optimum of between5 and 9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307,Barbesgoard et al, issued March 6, 1984, which discloses fungalcellulase produced from Humicola insolens and Humicola strain DSM1800 ora cellulase 212-producing fungus belonging to the genus Aeromonas, andcellulase extracted from the hepatopancreas of a marine mollusk(Dolabella Auricula Solander), suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. In addition,cellulase especially suitable for use herein are disclosed in WO92-13057 (Procter & Gamble). Most preferably, the cellulases used in theinstant detergent compositions are purchased commercially from NOVOIndustries A/S under the product names CAREZYME® and CELLUZYME®.

Perfume

The detergent composition preferably comprises from about 0.001% toabout 5%, more preferably from about 0.01% to about 2%, and mostpreferably from about 0.2% to 0.7% by weight of a perfume as describedherein. The formulator has the luxury of choosing from a wide variety ofperfume ingredients in order to arrive at a perfume formulation withinthe definition stated previously. Several perfume formulations are setforth in Example I hereafter. The perfume formulations can be preparedfrom perfume ingredients including but not limited to:7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene;ionone methyl; ionone gamma methyl; methyl cedrylone; methyldihydrojasmonate; methyl 1,6, 10-trimethyl-2,5,9-cyclododecatrien-1-ylketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-butanone;benzophenone; methyl beta-naphthyl ketone;6-acetyl-1,1,2,3,3,5hexamethyl indane;5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal,4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde;7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-1-al; isohexenyl cyclohexylcarboxaldehyde; formyl tricyclodecane; condensation products ofhydroxycitronellal and methyl anthranilate, condensation products ofhydroxycitronellal and indol, condensation products of phenylacetaldehyde and indol;2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin;heliotropin; hexyl cinnamic aldehyde; amyl cinnamic aldehyde;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; coumarin;decalactone gamma; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acidlactone;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane;beta-naphthol methyl ether; ambroxane;dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan; cedrol,5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenylacetate; benzyl salicylate; cedryl acetate; and para-(tert-butyl)cyclohexyl acetate.

Particularly preferred perfume materials are those that provide thelargest odor improvements in finished product compositions containingcellulases. These perfumes include but are not limited to: hexylcinnamic aidehyde; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde;7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7tetramethyl naphthalene;benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate;beta-napthol methyl ether; methyl beta-naphthyl ketone;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyrane;dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]blfuran; anisaldehyde;coumarin; cedrol; vanillin; cyclopentadecanolide; tricyclodecenylacetate; and tricyclodecenyl propionate.

Other perfume materials include essential oils, resinoids, and resinsfrom a variety of sources including but not limited to orange oil, lemonoil, patchouli, Peru balsam, Olibanum resinoid, styrax, labdanum resin,nutmeg, cassia oil, benzoin resin, coriander, lavandin and lavender.Still other perfume chemicals include phenyl ethyl alcohol, terpineol,linalool, linalyl acetate, geraniol, nerol,2-(1,1-dimethylethyl)cyclohexanol acetate, benzyl acetate, orangeterpenes, eugenol, diethylphthalate.

Detersive Surfactants

Preferably, the detergent composition comprises from about 1% to about55%, more preferably from about 15 to 40%, by weight, of a detersivesurfactant. Nonlimiting examples of surfactants useful herein includethe conventional C₁₁ -C₁₈ alkyl benzene sulfonates ("LAS") and primary,branched-chain and random C₁₀ -C₂₀ alkyl sulfates ("AS"), the C₁₀ -C₁₈secondary (2,3) alkyl sulfates of the formula CH₃ (CH₂)_(x) (CHOSO₃ ⁻M⁺)CH₃ and CH₃ (CH₂)_(y) (CHOSO₃ ^(-M) ⁺) CH₂ CH₃ where x and (y+1) areintegers of at least about 7, preferably at least about 9, and M is awater-solubilizing cation, especially sodium, unsaturated sulfates suchas oleyl sulfate, the C₁₀ -C₁₈ alkyl alkoxy sulfates ("AE_(x) S";especially EO 1-7 ethoxy sulfates), C₁₀ -C₁₈ alkyl alkoxy carboxylates(especially the EO 1-5 ethoxycarboxylates), the C₁₀₋₁₈ glycerol ethers,the C₁₀ -C₁₈ alkyl polyglycosides and their corresponding sulfatedpolyglycosides, and C₁₂ -C₁₈ alpha-sulfonated fatty acid esters. Ifdesired, the conventional nonionic and amphoteric surfactants such asthe C₁₂ -C₁₈ alkyl ethoxylates ("AE") including the so-called narrowpeaked alkyl ethoxylates and C₆ -C₁₂ alkyl phenol alkoxylates(especially ethoxylates and mixed ethoxy/propoxy), C₁₂ -C₁₈ betaines andsulfobetaines ("sultaines"), C₁₀ -C₁₈ amine oxides, and the like, canalso be included in the overall compositions. The C₁₀ -C₁₈ N-alkylpolyhydroxy fatty acid amides can also be used. Typical examples includethe C₁₂ -C₁₈ N-methylglucamides. See WO 9,206,154. Other sugar-derivedsurfactants include the N-alkoxy polyhydroxy fatty acid amides, such asC₁₀ -C₁₈ N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C₁₂-C₁₈ glucamides can be used for low sudsing. C₁₀ -C₂₀ conventional soapsmay also be used. If high sudsing is desired, the branched-chain C₁₀-C.sub. 16 soaps may be used. Mixtures of anionic and nonionicsurfactants are especially useful. Other conventional useful surfactantsare listed in standard texts.

The C₁₀ -C₁₈ alkyl alkoxy sulfates ("AE_(x) S"; especially EO 1-7 ethoxysulfates) and C₁₂ -C₁₈ alkyl ethoxylates ("ALE") are the most preferredfor the cellulase-containing detergents described herein.

Detergency Builders

Detergent builders can optionally be included in the compositions hereinto assist in controlling mineral hardness. Inorganic as well as organicbuilders can be used. Builders are typically used in fabric launderingcompositions to assist in the removal of particulate soils.

The level of builder can vary widely depending upon the end use of thecomposition and its desired physical form. When present, thecompositions will typically comprise at least about 1% builder. Liquidformulations typically comprise from about 5% to about 50%, moretypically about 5% to about 30%, by weight, of detergent builder.Granular formulations typically comprise from about 10% to about 80%,more typically from about 15% to about 50% by weight, of the detergentbuilder. Lower or higher levels of builder, however, are not meant to beexcluded.

Inorganic or P-containing detergent builders include, but are notlimited to, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (exemplified by the tripolyphosphates, pyrophosphates,and glassy polymeric meta-phosphates), phosphonates, phytic acid,silicates, carbonates (including bicarbonates and sesquicarbonates),sulphates, and aluminosilicates. However, non-phosphate builders arerequired in some locales. Importantly, the compositions herein functionsurprisingly well even in the presence of the so-called "weak" builders(as compared with phosphates) such as citrate, or in the so-called"underbuilt" situation that may occur with zeolite or layered silicatebuilders.

Examples of silicate builders are the alkali metal silicates,particularly those having a SiO₂ :Na₂ O ratio in the range 1.6:1 to3.2:1 and layered silicates, such as the layered sodium silicatesdescribed in U.S. Pat. No. 4,664,839, issued May 12, 1987 to H. P.Rieck. NaSKS6 is the trademark for a crystalline layered silicatemarketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlikezeolite builders, the Na SKS-6 silicate builder does not containaluminum. NaSKS-6 has the delta-Na₂ SiO₅ morphology form of layeredsilicate. It can be prepared by methods such as those described inGerman DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferredlayered silicate for use herein, but other such layered silicates, suchas those having the general formula NaMSi_(x) O_(2x+1).yH₂ O wherein Mis sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and yis a number from 0 to 20, preferably 0 can be used herein. Various otherlayered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, asthe alpha, beta and gamma forms. As noted above, the delta-Na₂ SiO₅(NaSKS-6 form) is most preferred for use herein. Other silicates mayalso be useful such as for example magnesium silicate, which can serveas a crispening agent in granular formulations, as a stabilizing agentfor oxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973.

Aluminosilicate builders are useful in the present invention.Aluminosilicate builders are of great importance in most currentlymarketed heavy duty granular detergent compositions, and can also be asignificant builder ingredient in liquid detergent formulations.Aluminosilicate builders include those having the empirical formula:

    M.sub.z [(zAlO.sub.2).sub.y ].xH.sub.2 O

wherein z and y are integers of at least 6, the molar ratio of z to y isin the range from 1.0 to about 0.5, and x is an integer from about 15 toabout 264.

Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturally-occurring aluminosilicates orsynthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel, etal, issued October 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials useful herein are available underthe designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. Inan especially preferred embodiment, the crystalline aluminosilicate ionexchange material has the formula:

    Na.sub.12 [(AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ].xH.sub.2 O

wherein x is from about 20 to about 30, especially about 27. Thismaterial is known as Zeolite A. Dehydrated zeolites (x=0-10) may also beused herein. Preferably, the aluminosilicate has a particle size ofabout 0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the presentinvention include, but are not restricted to, a wide variety ofpolycarboxylate compounds. As used herein, "polycarboxylate" refers tocompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Polycarboxylate builder can generally be added to thecomposition in acid form, but can also be added in the form of aneutralized salt. When utilized in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categoriesof useful materials. One important category of polycarboxylate buildersencompasses the ether polycarboxylates, including oxydisuccinate, asdisclosed in Berg, U.S. Pat. No. 3,128,287, issued April 7, 1964, andLamberti et al, U.S. Pat. No. 3,635,830, issued Jan. 18, 1972. See also"TMS/TDS" builders of U.S. Pat. No. 4,663,071, issued to Bush et al, onMay 5, 1987. Suitable ether polycarboxylates also include cycliccompounds, particularly alicyclic compounds, such as those described inU.S. Pat. No. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonicacid, and carboxymethyloxysuccinic acid, the various alkali metal,ammonium and substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxydisuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt, are polycarboxylate builders of particularimportance for heavy duty liquid detergent formulations due to theiravailability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially incombination with aeolite and/or layered silicate builders.Oxydisuccinates are also especially useful in such compositions andcombinations.

Also suitable in the detergent compositions of the present invention arethe 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986. Usefulsuccinic acid builders include the C₅ -C₂₀ alkyl and alkenyl succinicacids and salts thereof. A particularly preferred compound of this typeis dodecenylsuccinic acid. Specific examples of succinate buildersinclude: laurylsuccinate, myristylsuccinate, palmitylsuccinate,2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.Laurylsuccinates are the preferred builders of this group, and aredescribed in European Patent Application 86200690.5/0,200,263, publishedNov. 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al, issued Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S. Pat. No.3,723,322.

Fatty acids, e.g., C₁₂ -C₁₈ monocarboxylic acids, can also beincorporated into the compositions alone, or in combination with theaforesaid builders, especially citrate and/or the succinate builders, toprovide additional builder activity. Such use of fatty acids willgenerally result in a diminution of sudsing, which should be taken intoaccount by the formulator.

In situations where phosphorus-based builders can be used, andespecially in the formulation of bars used for hand-launderingoperations, the various alkali metal phosphates such as the well-knownsodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphatecan be used. Phosphonate builders such asethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see,for example, U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148and 3,422,137) can also be used.

Adjunct Ingredients

The compositions herein can optionally include one or more otherdetergent adjunct materials or other materials for assisting orenhancing cleaning performance, treatment of the substrate to becleaned, or to modify the aesthetics of the detergent composition (e.g.,colorants, dyes, etc.). The following are illustrative examples of suchadjunct materials.

Other Enzymes--Additional enzymes can be included in the formulationsherein for a wide variety of fabric laundering purposes, includingremoval of protein-based, carbohydrate-based, or triglyceride-basedstains, for example, and for the prevention of refugee dye transfer, andfor fabric restoration. The additional enzymes to be incorporatedinclude proteases, amylases, lipases, and peroxidases, as well asmixtures thereof. Other types of enzymes may also be included. They maybe of any suitable origin, such as vegetable, animal, bacterial, fungaland yeast origin. However, their choice is governed by several factorssuch as pH-activity and/or stability optima, thermostability, stabilityversus active detergents, builders as well as their potential to causemalodors during use. In this respect bacterial or fungal enzymes arepreferred, such as bacterial amylases and proteases.

Enzymes are normally incorporated at levels sufficient to provide up toabout 5 mg by weight, more typically about 0.01 mg to about 3 mg, ofactive enzyme per gram of the composition. Stated otherwise, thecompositions herein will typically comprise from about 0.001% to about5%, preferably 0.01%-1% by weight of a commercial enzyme preparation.Protease enzymes are usually present in such commercial preparations atlevels sufficient to provide from 0.005 to 0.1 Anson units (AU) ofactivity per gram of composition.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniforms. Anothersuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold by NovoIndustries A/S under the registered trade name ESPERASE. The preparationof this enzyme and analogous enzymes is described in British PatentSpecification No. 1,243,784 of Novo. Proteolytic enzymes suitable forremoving protein-based stains that are commercially available includethose sold under the trade names ALCALASE and SAVINASE by NovoIndustries A/S (Denmark) and MAXATASE by International Bio-Synthetics,Inc. (The Netherlands). Other proteases include Protease A (see EuropeanPatent Application 130,756, published Jan. 9, 1985); Protease B (seeEuropean Patent Application Serial No. 87303761.8, filed Apr. 28, 1987,and European Patent Application 130,756, Bott et al, published Jan. 9,1985); and proteases made by Genencor International, Inc., according toone or more of the following patents: Caldwell et al, U.S. Pat. Nos.5,185,258, 5,204,015 and 5,244,791.

Amylases include, for example, α-amylases described in British PatentSpecification No. 1,296,839 (Novo), RAPIDASE, InternationalBio-Synthetics, Inc. and TERMAMYL, Novo Industries.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in British Patent 1,372,034. See also lipasesin Japanese Patent Application 53,20487, laid open to public inspectionon Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co.Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafterreferred to as "Amano-P." Other commercial lipases include Amano-CES,lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.lipolyticurn NRRLB 3673, commercially available from Toyo Jozo Co.,Tagata, Japan; and further Chromobacter viscosum lipases from U.S.Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipasesex Pseudomonas gladloll. The LIPOLASE enzyme derived from Hutnicolalanuginosa and commercially available from Novo (see also EPO 341,947)is a preferred lipase for use herein.

Peroxidase enzymes are used in combination with oxygen sources, e.g.,percarbonate, perborate, persulfate, hydrogen peroxide, etc. They areused for "solution bleaching," i.e. to prevent transfer of dyes orpigments removed from substrates during wash operations to othersubstrates in the wash solution. Peroxidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in PCT International Application WO 89/099813, published Oct. 19, 1989,by O. Kirk, assigned to Novo Industries A/S.

A wide range of enzyme materials and means for their incorporation intosynthetic detergent compositions are also disclosed in U.S. Pat. No.3,553,139, issued Jan. 5, 1971 to McCarty et al. Enzymes are furtherdisclosed in U.S. Pat. No. 4,101,457, Place et al, issued July 18, 1978,and in U.S. Pat. No. 4,507,219, Hughes, issued Mar. 26, 1985, both.Enzyme materials useful for liquid detergent formulations, and theirincorporation into such formulations, are disclosed in U.S. Pat. No.4,261,868, Hora et al, issued Apr. 14, 1981. Enzymes for use indetergents can be stabilized by various techniques. Typical granular orpowdered detergents can be stabilized effectively by using enzymegranuletes. Enzyme stabilization techniques are disclosed andexemplified in U.S. Pat. No. 3,600,319, issued Aug. 17, 1971 to Gedge,et al, and European Patent Application Publication No. 0 199 405,Application No. 86200586.5, published Oct. 29, 1986, Venegas. Enzymestabilization systems are also described, for example, in U.S. Pat. No.3,519,570.

Enzyme Stabilizers - The enzymes employed herein are stabilized by thepresence of water-soluble sources of calcium and/or magnesium ions inthe finished compositions which provide such ions to the enzymes.(Calcium ions are generally somewhat more effective than magnesium ionsand are preferred herein if only one type of cation is being used.)Additional stability can be provided by the presence of various otherart-disclosed stabilizers, especially borate species: see Severson, U.S.Pat. No. 4,537,706. Typical detergents, especially liquids, willcomprise from about 1 to about 30, preferably from about 2 to about 20,more preferably from about 5 to about 15, and most preferably from about8 to about 12, millimoles of calcium ion per liter of finishedcomposition. This can vary somewhat, depending on the amount of enzymepresent and its response to the calcium or magnesium ions. The level ofcalcium or magnesium ions should be selected so that there is alwayssome minimum level available for the enzyme, after allowing forcomplexation with builders, fatty acids, etc., in the composition. Anywater-soluble calcium or magnesium salt can be used as the source ofcalcium or magnesium ions, including, but not limited to, calciumchloride, calcium sulfate, calcium malate, calcium maleate, calciumhydroxide, calcium formate, and calcium acetate, and the correspondingmagnesium salts. A small amount of calcium ion, generally from about0.05 to about 0.4 millimoles per liter, is often also present in thecomposition due to calcium in the enzyme slurry and formula water. Insolid detergent compositions the formulation may include a sufficientquantity of a water-soluble calcium ion source to provide such amountsin the laundry liquor. In the alternative, natural water hardness maysuffice.

It is to be understood that the foregoing levels of calcium and/ormagnesium ions are sufficient to provide enzyme stability. More calciumand/or magnesium ions can be added to the compositions to provide anadditional measure of grease removal performance. Accordingly, as ageneral proposition the compositions herein will typically comprise fromabout 0.05% to about 2% by weight of a water-soluble source of calciumor magnesium ions, or both. The amount can vary, of course, with theamount and type of enzyme employed in the composition.

The compositions herein may also optionally, but preferably, containvarious additional stabilizers, especially borate-type stabilizers.Typically, such stabilizers will be used at levels in the compositionsfrom about 0.25% to about 10%, preferably from about 0.5% to about 5%,more preferably from about 0.75% to about 3%, by weight of boric acid orother borate compound capable of forming boric acid in the composition(calculated on the basis of boric acid). Boric acid is preferred,although other compounds such as boric oxide, borax and other alkalimetal borates (e.g., sodium ortho-, meta- and pyroborate, and sodiumpentaborate) are suitable. Substituted boric acids (e.g., phenylboronicacid, butane boronic acid, and p-bromo phenylboronic acid) can also beused in place of boric acid.

Bleaching Compounds--Bleaching Agents and Bleach Activators--Thedetergent compositions herein may optionally contain bleaching agents orbleaching compositions containing a bleaching agent and one or morebleach activators. When present, bleaching agents will typically be atlevels of from about 1% to about 30%, more typically from about 5% toabout 20%, of the detergent composition, especially for fabriclaundering. If present, the amount of bleach activators will typicallybe from about 0.1% to about 60%, more typically from about 0.5% to about40% of the bleaching composition comprising the bleachingagent-plus-bleach activator.

The bleaching agents used herein can be any of the bleaching agentsuseful for detergent compositions in textile cleaning, hard surfacecleaning, or other cleaning purposes that are now known or become known.These include oxygen bleaches as well as other bleaching agents.Perborate bleaches, e.g., sodium perborate (e.g., mono- ortetra-hydrate) can be used herein.

Another category of bleaching agent that can be used without restrictionencompasses percarboxylic acid bleaching agents and salts thereof.Suitable examples of this class of agents include magnesiummonoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid anddiperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S.Pat. No. 4,483,781, Hartman, issued Nov. 20, 1984, U.S. patentapplication No. 740,446, Burns et al, filed June 3, 1985, EuropeanPatent Application 0,133,354, Banks et al, published Feb. 20, 1985, andU.S. Pat. No. 4,412,934, Chung et al, issued Nov. 1, 1983. Highlypreferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproicacid as described in U.S. Pat. No. 4,634,551, issued Jan. 6, 1987 toBurns et al.

Peroxygen bleaching agents can also be used. Suitable peroxygenbleaching compounds include sodium carbonate peroxyhydrate andequivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate,urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE,manufactured commercially by DuPont) can also be used.

A preferred percarbonate bleach comprises dry particles having anaverage particle size in the range from about 500 micrometers to about1,000 micrometers, not more than about 10% by weight of said particlesbeing smaller than about 200 micrometers and not more than about 10% byweight of said particles being larger than about 1,250 micrometers.Optionally, the percarbonate can be coated with silicate, borate orwater-soluble surfactants. Percarbonate is available from variouscommercial sources such as FMC, Solvay and Tokai Denka.

Mixtures of bleaching agents can also be used.

Peroxygen bleaching agents, the perborates, the percarbonates, etc., arepreferably combined with bleach activators, which lead to the in situproduction in aqueous solution (i.e., during the washing process) of theperoxy acid corresponding to the bleach activator. Various nonlimitingexamples of activators are disclosed in U.S. Pat. No. 4,915,854, issuedApr. 10, 1990 to Mao et al, and U.S. Pat. No. 4,412,934. Thenonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine(TAED) activators are typical, and mixtures thereof can also be used.See also U.S. Pat. No. 4,634,551 for other typical bleaches andactivators useful herein.

Highly preferred amido-derived bleach activators are those of theformulae:

    R.sup.1 N(R.sup.5)C(O)R.sup.2 C(O)L or R.sup.1 C(O)N(R.sup.5)R.sup.2 C(O)L

wherein R¹ is an alkyl group containing from about 6 to about 12 carbonatoms, R² is an alkylene containing from 1 to about 6 carbon atoms, R⁵is H or alkyl, aryl, or alkaryl containing from about 1 to about 10carbon atoms, and L is any suitable leaving group. A leaving group isany group that is displaced from the bleach activator as a consequenceof the nucleophilic attack on the bleach activator by the perhydrolysisanion. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators of the above formulae include(6-octanamidocaproyl)oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate,(6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof asdescribed in U.S. Pat. No. 4,634,551, incorporated herein by reference.

Another class of bleach activators comprises the benzoxazin-typeactivators disclosed by Hodge et al in U.S. Pat. No. 4,966,723, issuedOct. 30, 1990, incorporated herein by reference. A highly preferredactivator of the benzoxazin-type is: ##STR1##

Still another class of preferred bleach activators includes the acyllactam activators, especially acyl caprolactams and acyl valerolactamsof the formulae: ##STR2## wherein R⁶ is H or an alkyl, aryl, alkoxyaryl,or alkaryl group containing from 1 ;l to about 12 carbon atoms. Highlypreferred lactam activators include benzoyl caprolactam, octanoylcaprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam,decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam,octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam,nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixturesthereof. See also U.S. Pat. No. 4,545,784, issued to Sanderson, Oct. 8,1985, incorporated herein by reference, which discloses acylcaprolactams, including benzoyl caprolactam, adsorbed into sodiumperborate.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein. One type of non-oxygen bleachingagent of particular interest includes photoactivated bleaching agentssuch as the sulfonated zinc and/or aluminum phthalocyanines. See U.S.Pat. No. 4,033,718, issued July 5, 1977 to Holcombe et al. If used,detergent compositions will typically contain from about 0.025% to about1.25%, by weight, of such bleaches, especially sulfonate zincphthalocyanine.

If desired, the bleaching compounds can be catalyzed by means of amanganese compound. Such compounds are well known in the art andinclude, for example, the manganese-based catalysts disclosed in U.S.Pat. Nos. 5,246,621, 5,244,594; 5,194,416; 5,114,606; and European Pat.App. Pub. Nos. 549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferredexamples of these catalysts include Mn^(IV) ₂ (u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (PF₆)₂, Mn^(III) ₂ (u-O)₁(u-OAc)₂ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂₋ (ClO₄)₂, Mn^(IV) ₄(u-O)₆ (1,4,7-triazacyclononane)₄ (ClO₄)₄, Mn^(III) Mn^(IV) ₄ (u-O)₁(u-OAc)₂₋ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (ClO₄)₃, Mn^(IV)(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃ (PF₆), and mixturesthereof. Other metal-based bleach catalysts include those disclosed inU.S. Pat. Nos. 4,430,243 and 5,114,611. The use of manganese withvarious complex ligands to enhance bleaching is also reported in thefollowing U.S. Pat. Nos. 4,728,455; 5,284,944; 5,246,612; 5,256,779;5,280,117; 5,274,147; 5,153,161; 5,227,084.

As a practical matter, and not by way of limitation, the compositionsand processes herein can be adjusted to provide on the order of at leastone part per ten million of the active bleach catalyst species in theaqueous washing liquor, and will preferably provide from about 0.1 ppmto about 700 ppm, more preferably from about 1 ppm to about 500 ppm, ofthe catalyst species in the laundry liquor.

Polymeric Soil Release Agent--Any polymeric soil release agent known tothose skilled in the art can optionally be employed in the compositionsand processes of this invention. Polymeric soil release agents arecharacterized by having both hydrophilic segments, to hydrophilize thesurface of hydrophobic fibers, such as polyester and nylon, andhydrophobic segments, to deposit upon hydrophobic fibers and remainadhered thereto through completion of washing and rinsing cycles and,thus, serve as an anchor for the hydrophilic segments. This can enablestains occurring subsequent to treatment with the soil release agent tobe more easily cleaned in later washing procedures.

The polymeric soil release agents useful herein especially include thosesoil release agents having: (a) one or more nonionic hydrophilecomponents consisting essentially of (i) polyoxyethylene segments with adegree of polymerization of at least 2, or (ii) oxypropylene orpolyoxypropylene segments with a degree of polymerization of from 2 to10, wherein said hydrophile segment does not encompass any oxypropyleneunit unless it is bonded to adjacent moieties at each end by etherlinkages, or (iii) a mixture of oxyalkylene units comprising oxyethyleneand from 1 to about 30 oxypropylene units wherein said mixture containsa sufficient amount of oxyethylene units such that the hydrophilecomponent has hydrophilicity great enough to increase the hydrophilicityof conventional polyester synthetic fiber surfaces upon deposit of thesoil release agent on such surface, said hydrophile segments preferablycomprising at least about 25% oxyethylene units and more preferably,especially for such components having about 20 to 30 oxypropylene units,at least about 50% oxyethylene units; or (b) one or more hydrophobecomponents comprising (i) C₃ oxyalkylene terephthalate segments,wherein, if said hydrophobe components also comprise oxyethyleneterephthalate, the ratio of oxyethylene terephthalate:C₃ oxyalkyleneterephthalate units is about 2:1 or lower, (ii) C₄ -C₆ alkylene or oxyC₄ -C₆ alkylene segments, or mixtures therein, (iii) poly (vinyl ester)segments, preferably polyvinyl acetate), having a degree ofpolymerization of at least 2, or (iv) C₁ -C₄ alkyl ether or C₄hydroxyalkyl ether substituents, or mixtures therein, wherein saidsubstituents are present in the form of C₁ -C₄ alkyl ether or C₄hydroxyalkyl ether cellulose derivatives, or mixtures therein, and suchcellulose derivatives are amphiphilic, whereby they have a sufficientlevel of C₁ -C₄ alkyl ether and/or C₄ hydroxyalkyl ether units todeposit upon conventional polyester synthetic fiber surfaces and retaina sufficient level of hydroxyls, once adhered to such conventionalsynthetic fiber surface, to increase fiber surface hydrophilicity, or acombination of (a) and (b).

Typically, the polyoxyethylene segments of (a)(i) will have a degree ofpolymerization of from about 200, although higher levels can be used,preferably from 3 to about 150, more preferably from 6 to about 100.Suitable oxy C₄ -C₆ alkylene hydrophobe segments include, but are notlimited to, end-caps of polymeric soil release agents such as MO₃S(CH₂)_(n) OCH₂ CH₂ O--, where M is sodium and n is an integer from 4-6as disclosed in U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 toGosselink.

Polymeric soil release agents useful in the present invention alsoinclude cellulosic derivatives such as hydroxyether cellulosic polymers,copolymeric blocks of ethylene terephthalate or propylene terephthalatewith polyethylene oxide or polypropylene oxide terephthalate, and thelike. Such agents are commercially available and include hydroxyethersof cellulose such as METHOCEL (Dow). Cellulosic soil release agents foruse herein also include those selected from the group consisting of C₁-C₄ alkyl and C₄ hydroxyalkyl cellulose; see U.S. Pat. No. 4,000,093,issued Dec. 28, 1976 to Nicol, et al.

Soil release agents characterized by poly(vinyl ester) hydrophobesegments include graft copolymers of poly(vinyl ester), e.g., C₁ -C₆vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkyleneoxide backbones, such as polyethylene oxide backbones. See EuropeanPatent Application 0 219 048, published Apr. 22, 1987 by Kud, et al.Commercially available soil release agents of this kind include theSOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (WestGermany).

One type of preferred soil release agent is a copolymer having randomblocks of ethylene terephthalate and polyethylene oxide (PEO)terephthalate. The molecular weight of this polymeric soil release agentis in the range of from about 25,000 to about 55,000. See U.S. Pat. No.3,959,230 to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 toBasadur issued Jul. 8, 1975.

Another preferred polymeric soil release agent is a polyester withrepeat units of ethylene terephthalate units contains 10-15% by weightof ethylene terephthalate units together with 90-80% by weight ofpolyoxyethylene terephthalate units, derived from a polyoxyethyleneglycol of average molecular weight 300-5,000. Examples of this polymerinclude the commercially available material ZELCON 5126 (from DuPont)and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct.27, 1987 to Gosselink.

Another preferred polymeric soil release agent is a sulfonated productof a substantially linear ester oligomer comprised of an oligomericester backbone of terephthaloyl and oxyalkyleneoxy repeat units andterminal moieties covalently attached to the backbone. These soilrelease agents are described fully in U.S. Pat. No. 4,968,451, issuedNov. 6, 1990 to J. J. Scheibel and E. P. Gosselink. Other suitablepolymeric soil release agents include the terephthalate polyesters ofU.S. Pat. No. 4,711,730, issued Dec. 8, 1987 to Gosselink et al, theanionic end-capped oligomeric esters of U.S. Pat. No. 4,721,580, issuedJan. 26, 1988 to Gosselink, and the block polyester oligomeric compoundsof U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.

Preferred polymeric soil release agents also include the soil releaseagents of U.S. Pat. No. 4,877,896, issued Oct. 31, 1989 to Maldonado etal, which discloses anionic, especially sulfoaroyl, end-cappedterephthalate esters. Still another preferred soil release agent is anoligomer with repeat units of terephthaloyl units, sulfoisoterephthaloylunits, oxyethyleneoxy and oxy-1,2-propylene units. The repeat units formthe backbone of the oligomer and are preferably terminated with modifiedisethionate end-caps. A particularly preferred soil release agent ofthis type comprises about one sulfoisophthaloyl unit, 5 terephthaloylunits, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of fromabout 1.7 to about 1.8, and two end-cap units of sodium2-(2-hydroxyethoxy)-ethanesulfonate. Said soil release agent alsocomprises from about 0.5% to about 20%, by weight of the oligomer, of acrystalline-reducing stabilizer, preferably selected from the groupconsisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, andmixtures thereof.

If utilized, soil release agents will generally comprise from about0.01% to about 10.0%, by weight, of the detergent compositions herein,typically from about 0.1% to about 5%, preferably from about 0.2% toabout 3.0%.

Chelating Agents - The detergent compositions herein may also optionallycontain one or more iron and/or manganese chelating agents. Suchchelating agents can be selected from the group consisting of aminocarboxylates, amino phosphonates, polyfunctionally-substituted aromaticchelating agents and mixtures therein, all as hereinafter defined.Without intending to be bound by theory, it is believed that the benefitof these materials is due in part to their exceptional ability to removeiron and manganese ions from washing solutions by formation of solublechelates.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetraproprionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at lease low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred,these amino phosphonates to not contain alkyl or alkenyl groups withmore than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21,1974, to Connor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate ("EDDS"), especially the [S,S]isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

If utilized, these chelating agents will generally comprise from about0.1% to about 10% by weight of the detergent compositions herein. Morepreferably, if utilized, the chelating agents will comprise from about0.1% to about 3.0% by weight of such compositions.

Clay Soil Removal/Anti-redeposition Agents - The compositions of thepresent invention can also optionally contain water-soluble ethoxylatedamines having clay soil removal and antiredeposition properties.Granular detergent compositions which contain these compounds typicallycontain from about 0.01% to about 10.0% by weight of the water-solubleethoxylates amines; liquid detergent compositions typically containabout 0.01% to about 5%.

The most preferred soil release and anti-redeposition agent isethoxylated tetraethylenepentamine. Exemplary ethoxylated amines arefurther described in U.S. Pat. No. 4,597,898, VanderMeer, issued Jul. 1,1986. Another group of preferred clay soil removal-antiredepositionagents are the cationic compounds disclosed in European PatentApplication 111,965, Oh and Gosselink, published Jun. 27, 1984. Otherclay soil removal/antiredeposition agents which can be used include theethoxylated amine polymers disclosed in European Patent Application111,984, Gosselink, published Jun. 27, 1984; the zwitterionic polymersdisclosed in European Patent Application 112,592, Gosselink, publishedJul. 4, 1984; and the amine oxides disclosed in U.S. Pat. No. 4,548,744,Connor, issued Oct. 22, 1985. Other clay soil removal and/or antiredeposition agents known in the art can also be utilized in thecompositions herein. Another type of preferred antiredeposition agentincludes the carboxy methyl cellulose (CMC) materials. These materialsare well known in the art.

Polymeric Dispersing Agents - Polymeric dispersing agents canadvantageously be utilized at levels from about 0.1% to about 7%, byweight, in the compositions herein, especially in the presence ofzeolite and/or layered silicate builders. Suitable polymeric dispersingagents include polymeric polycarboxylates and polyethylene glycols,although others known in the art can also be used. It is believed,though it is not intended to be limited by theory, that polymericdispersing agents enhance overall detergent builder performance, whenused in combination with other builders (including lower molecularweight polycarboxylates) by crystal growth inhibition, particulate soilrelease peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing orcopolymerizing suitable unsaturated monomers, preferably in their acidform. Unsaturated monomeric acids that can be polymerized to formsuitable polymeric polycarboxylates include acrylic acid, maleic acid(or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. The presencein the polymeric polycarboxylates herein or monomeric segments,containing no carboxylate radicals such as vinylmethyl ether, styrene,ethylene, etc. is suitable provided that such segments do not constitutemore than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived fromacrylic acid. Such acrylic acid-based polymers which are useful hereinare the water-soluble salts of polymerized acrylic acid. The averagemolecular weight of such polymers in the acid form preferably rangesfrom about 2,000 to 10,000, more preferably from about 4,000 to 7,000and most preferably from about 4,000 to 5,000. Water-soluble salts ofsuch acrylic acid polymers can include, for example, the alkali metal,ammonium and substituted ammonium salts. Soluble polymers of this typeare known materials. Use of polyacrylates of this type in detergentcompositions has been disclosed, for example, in Diehi, U.S. Pat. No.3,308,067, issued Mar. 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferredcomponent of the dispersing/anti-redeposition agent. Such materialsinclude the water-soluble salts of copolymers of acrylic acid and maleicacid. The average molecular weight of such copolymers in the acid formpreferably ranges from about 2,000 to 100,000, more preferably fromabout 5,000 to 75,000, most preferably from about 7,000 to 65,000. Theratio of acrylate to maleate segments in such copolymers will generallyrange from about 30:1 to about 1:1, more preferably from about 10:1 to2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers caninclude, for example, the alkali metal, ammonium and substitutedammonium salts. Soluble acrylate/maleate copolymers of this type areknown materials which are described in European Patent Application No.66915, published Dec. 15, 1982, as well as in EP 193,360, publishedSept. 3, 1986, which also describes such polymers comprisinghydroxypropylacrylate. Still other useful dispersing agents include themaleic/acrylic/vinyl alcohol terpolymers. Such materials are alsodisclosed in EP 193,360, including, for example, the 45/45/10 terpolymerof acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol(PEG). PEG can exhibit dispersing agent performance as well as act as aclay soil removal-antiredeposition agent. Typical molecular weightranges for these purposes range from about 500 to about 100,000,preferably from about 1,000 to about 50,000, more preferably from about1,500 to about 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used,especially in conjunction with zeolite builders. Dispersing agents suchas polyaspartate preferably have a molecular weight (avg.) of about10,000.

Brightener - Any optical brighteners or other brightening or whiteningagents known in the art can be incorporated at levels typically fromabout 0.05% to about 1.2%, by weight, into the detergent compositionsherein. Commercial optical brighteners which may be useful in thepresent invention can be classified into subgroups, which include, butare not necessarily limited to, derivatives of stilbene, pyrazoline,coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide,azoles, 5- and 6-membered-ring heterocycles, and other miscellaneousagents. Examples of such brighteners are disclosed in "The Productionand Application of Fluorescent Brightening Agents", M. Zahradnik,Published by John Wiley & Sons, New York (1982).

Specific examples of optical brighteners which are useful in the presentcompositions are those identified in U.S. Pat. No. 4,790,856, issued toWixon on Dec. 13, 1988. These brighteners include the PHORWHITE seriesof brighteners from Verona. Other brighteners disclosed in thisreference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; availablefrom Ciba-Geigy; Artic White CC and Artic White CWD, available fromHilton-Davis, located in Italy; the2-(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)-stil- benes; 4,4'-bis(stryl)bisphenyls; and theaminocoumarins. Specific examples of these brighteners include4-methyl-7-diethyl- amino coumarin; 1,2-bis(-venzimidazol-2-yl)ethylene;1,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene;2-stryl-napth-[1,2-d]oxazole; and2-(stilbene-4-yl)-2H-naphtho-[1,2-d]triazole. See also U.S. Pat. No.3,646,015, issued Feb. 29, 1972 to Hamilton. Anionic brighteners arepreferred herein.

Dye Transfer Inhibiting Agents - The compositions of the presentinvention may also include one or more materials effective forinhibiting the transfer of dyes from one fabric to another during thecleaning process. Generally, such dye transfer inhibiting agents includepolyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymersof N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,peroxidases, and mixtures thereof. If used, these agents typicallycomprise from about 0.01% to about 10% by weight of the composition,preferably from about 0.01% to about 5%, and more preferably from about0.05% to about 2%.

More specifically, the polyamine N-oxide polymers preferred for useherein contain units having the following structural formula: R-A_(x)-P; wherein P is a polymerizable unit to which an N-O group can beattached or the N-O group can form part of the polymerizable unit or theN-O group can be attached to both units; A is one of the followingstructures: --NC(O)--, --C(O)O--, --S--, --O--, --N=; x is 0 or 1; and Ris aliphatic, ethoxylated aliphatics, aromatics, heterocyclic oralicyclic groups or any combination thereof to which the nitrogen of theN-O group can be attached or the N-O group is part of these groups.Preferred polyamine N-oxides are those wherein R is a heterocyclic groupsuch as pyridine, pyrrole, imidazole, pyrrolidine, piperidine andderivatives thereof.

The N-O group can be represented by the following general structures:##STR3## wherein R₁, R₂, R₃ are aliphatic, aromatic, heterocyclic oralicyclic groups or combinations thereof; x, y and z are 0 or 1; and thenitrogen of the N-O group can be attached or form part of any of theaforementioned groups. The amine oxide unit of the polyamine N-oxideshas a pKa <10, preferably pKa <7, more preferred pKa <6.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof. These polymers include random or block copolymerswhere one monomer type is an amine N-oxide and the other monomer type isan N-oxide. The amine N-oxide polymers typically have a ratio of amineto the amine N-oxide of 10:1 to 1:1,000,000. However, the number ofamine oxide groups present in the polyamine oxide polymer can be variedby appropriate copolymerization or by an appropriate degree ofN-oxidation. The polyamine oxides can be obtained in almost any degreeof polymerization. Typically, the average molecular weight is within therange of 500 to 1,000,000; more preferred 1,000 to 500,000; mostpreferred 5,000 to 100,000. This preferred class of materials can bereferred to as "PVNO".

The most preferred polyamine N-oxide useful in the detergentcompositions herein is poly(4-vinylpyridine-N-oxide) which as an averagemolecular weight of about 50,000 and an amine to amine N-oxide ratio ofabout 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referredto as a class as "PVPVI") are also preferred for use herein. Preferablythe PVPVI has an average molecular weight range from 5,000 to 1,000,000,more preferably from 5,000 to 200,000, and most preferably from 10,000to 20,000. (The average molecular weight range is determined by lightscattering as described in Barth, et al., Chemical Analysis, Vol 113."Modern Methods of Polymer Characterization", the disclosures of whichare incorporated herein by reference.) The PVPVI copolymers typicallyhave a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1to 0.4:1. These copolymers can be either linear or branched.

The present invention compositions also may employ apolyvinylpyrrolidone ("PVP") having an average molecular weight of fromabout 5,000 to about 400,000, preferably from about 5,000 to about200,000, and more preferably from about 5,000 to about 50,000. PVP's areknown to persons skilled in the detergent field; see, for example,EP-A-262,897 and EP-A-256,696, incorporated herein by reference.Compositions containing PVP can also contain polyethylene glycol ("PEG")having an average molecular weight from about 500 to about 100,000,preferably from about 1,000 to about 10,000. Preferably, the ratio ofPEG to PVP on a ppm basis delivered in wash solutions is from about 2:1to about 50:1, and more preferably from about 3:1 to about 10:1.

The detergent compositions herein may also optionally contain from about0.005% to 5% by weight of certain types of hydrophilic opticalbrighteners which also provide a dye transfer inhibition action. Ifused, the compositions herein will preferably comprise from about 0.01%to 1% by weight of such optical brighteners.

The hydrophilic optical brighteners useful in the present invention arethose having the structural formula: ##STR4## wherein R₁ is selectedfrom anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R₂ is selectedfrom N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino,chloro and amino; and M is a salt-forming cation such as sodium orpotassium.

When in the above formula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl andM is a cation such as sodium, the brightener is4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the trade name Tinopal-UNPA-GX by Ciba-GeigyCorporation. Tinopal-UNPA-GX is the preferred hydrophilic opticalbrightener useful in the detergent compositions herein.

When in the above formula, R₁ is anilino, R₂ isN-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, thebrightener is4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R₁ is anilino, R₂ is morphilino and M is acation such as sodium, the brightener is4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the trade name Tinopal AMS-GX by Ciba Geigy Corporation.

The specific optical brightener species selected for use in the presentinvention provide especially effective dye transfer inhibitionperformance benefits when used in combination with the selectedpolymeric dye transfer inhibiting agents hereinbefore described. Thecombination of such selected polymeric materials (e.g., PVNO and/orPVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX,Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dyetransfer inhibition in aqueous wash solutions than does either of thesetwo detergent composition components when used alone. Without beingbound by theory, it is believed that such brighteners work this waybecause they have high affinity for fabrics in the wash solution andtherefore deposit relatively quick on these fabrics. The extent to whichbrighteners deposit on fabrics in the wash solution can be defined by aparameter called the "exhaustion coefficient". The exhaustioncoefficient is in general as the ratio of a) the brightener materialdeposited on fabric to b) the initial brightener concentration in thewash liquor. Brighteners with relatively high exhaustion coefficientsare the most suitable for inhibiting dye transfer in the context of thepresent invention.

Of course, it will be appreciated that other, conventional opticalbrightener types of compounds can optionally be used in the presentcompositions to provide conventional fabric "brightness" benefits,rather than a true dye transfer inhibiting effect. Such usage isconventional and well-known to detergent formulations.

Suds Suppressors--Compounds for reducing or suppressing the formation ofsuds can be incorporated into the compositions of the present invention.Suds suppression can be of particular importance in the so-called "highconcentration cleaning process" and in front-loading European-stylewashing machines.

A wide variety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category ofsuds suppressor of particular interest encompasses monocarboxylic fattyacid and soluble salts therein. See U.S. Pat. No. 2,954,347, issuedSept. 27, 1960 to Wayne St. John. The monocarboxylic fatty acids andsalts thereof used as suds suppressor typically have hydrocarbyl chainsof 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.Suitable salts include the alkali metal salts such as sodium, potassium,and lithium salts, and ammonium and alkanolammonium salts.

The detergent compositions herein may also contain non-surfactant sudssuppressors. These include, for example: high molecular weighthydrocarbons such as paraffin, fatty acid esters (e.g., fatty acidtriglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g., stearone), etc. Other suds inhibitors includeN-alkylated amino triazines such as tri- to hexaalkylmelamines or di- totetra-alkyldiamine chlortriazines formed as products of cyanuricchloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, and monostearylphosphates such as monostearyl alcohol phosphate ester and monostearyldi-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.The hydrocarbons such as paraffin and haloparaffin can be utilized inliquid form. The liquid hydrocarbons will be liquid at room temperatureand atmospheric pressure, and will have a pour point in the range ofabout -40° C. and about 50° C., and a minimum boiling point not lessthan about 110° C. (atmospheric pressure). It is also known to utilizewaxy hydrocarbons, preferably having a melting point below about 100° C.The hydrocarbons constitute a preferred category of suds suppressor fordetergent compositions. Hydrocarbon suds suppressors are described, forexample, in U.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolfo etal. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, andheterocyclic saturated or unsaturated hydrocarbons having from about 12to about 70 carbon atoms. The term "paraffin," as used in this sudssuppressor discussion, is intended to include mixtures of true paraffinsand cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors comprisessilicone suds suppressors. This category includes the use ofpolyorganosiloxane oils, such as polydimethylsiloxane, dispersions oremulsions of polyorganosiloxane oils or resins, and combinations ofpolyorganosiloxane with silica particles wherein the polyorganosiloxaneis chemisorbed or fused onto the silica. Silicone suds suppressors arewell known in the art and are, for example, disclosed in U.S. Pat. No.4,265,779, issued May 5, 1981 to Gandolfo et al and European PatentApplication No. 89307851.9, published Feb. 7, 1990, by Starch, M. S.

Other silicone suds suppressors are disclosed in U.S. Pat. No. 3,455,839which relates to compositions and processes for defoaming aqueoussolutions by incorporating therein small amounts of polydimethylsiloxanefluids.

Mixtures of silicone and silanated silica are described, for instance,in German Patent Application DOS 2,124,526. Silicone defoamers and sudscontrolling agents in granular detergent compositions are disclosed inU.S. Pat. No. 3,933,672, Bartolotta et al, and in U.S. Pat. No.4,652,392, Baginski et al, issued Mar. 24, 1987.

An exemplary silicone based suds suppressor for use herein is a sudssuppressing amount of a suds controlling agent consisting essentiallyof:

(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs.to about 1,500 cs. at 25° C.;

(ii) from about 5 to about 50 parts per 100 parts by weight of (i) ofsiloxane resin composed of (CH₃)₃ SiO_(1/2) units of SiO₂ units in aratio of from (CH₃)₃ SiO_(1/2) units and to SiO₂ units of from about0.6:1 to about 1.2:1; and

(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of asolid silica gel.

In the preferred silicone suds suppressor used herein, the solvent for acontinuous phase is made up of certain polyethylene glycols orpolyethylene-polypropylene glycol copolymers or mixtures thereof(preferred), or polypropylene glycol. The primary silicone sudssuppressor is branched/crosslinked and preferably not linear.

To illustrate this point further, typical liquid laundry detergentcompositions with controlled suds will optionally comprise from about0.001 to about 1, preferably from about 0.01 to about 0.7, mostpreferably from about 0.05 to about 0.5, weight % of said silicone sudssuppressor, which comprises (1) a nonaqueous emulsion of a primaryantifoam agent which is a mixture of (a) a polyorganosiloxane, (b) aresinous siloxane or a silicone resin-producing silicone compound, (c) afinely divided filler material, and (d) a catalyst to promote thereaction of mixture components (a), (b) and (c), to form silanolates;(2) at least one nonionic silicone surfactant; and (3) polyethyleneglycol or a copolymer of polyethylene-polypropylene glycol having asolubility in water at room temperature of more than about 2 weight %;and without polypropylene glycol. Similar amounts can be used ingranular compositions, gels, etc. See also U.S. Pat. No. 4,978,471,Starch, issued Dec. 18, 1990, and 4,983,316, Starch, issued Jan. 8,1991, 5,288,431, Huber et al., issued Feb. 22, 1994, and U.S. Pat. No.4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 throughcolumn 4, line 35.

The silicone suds suppressor herein preferably comprises polyethyleneglycol and a copolymer of polyethylene glycol/polypropylene glycol, allhaving an average molecular weight of less than about 1,000, preferablybetween about 100 and 800. The polyethylene glycol andpolyethylene/polypropylene copolymers herein have a solubility in waterat room temperature of more than about 2 weight %, preferably more thanabout 5 weight %.

The preferred solvent herein is polyethylene glycol having an averagemolecular weight of less than about 1,000, more preferably between about100 and 800, most preferably between 200 and 400, and a copolymer ofpolyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.Preferred is a weight ratio of between about 1:1 and 1:10, mostpreferably between 1:3 and 1:6, of polyethylene glycol:copolymer ofpolyethylene-polypropylene glycol.

The preferred silicone suds suppressors used herein do not containpolypropylene glycol, particularly of 4,000 molecular weight. They alsopreferably do not contain block copolymers of ethylene oxide andpropylene oxide, like PLURONIC L 101.

Other suds suppressors useful herein comprise the secondary alcohols(e.g., 2-alkyl alkanols) and mixtures of such alcohols with siliconeoils, such as the silicones disclosed in U.S. Pat. Nos. 4,798,679,4,075,118 and EP 150,872. The secondary alcohols include the C₆ -C₁₆alkyl alcohols having a C₁ -C₁₆ chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trademark ISOFOL 12.Mixtures of secondary alcohols are available under the trademarkISALCHEM 123 from Enichem. Mixed suds suppressors typically comprisemixtures of alcohol+silicone at a weight ratio of 1:5 to 5:1.

For any detergent compositions to be used in automatic laundry washingmachines, suds should not form to the extent that they overflow thewashing machine. Suds suppressors, when utilized, are preferably presentin a suds suppressing amount. By "suds suppressing amount" is meant thatthe formulator of the composition can select an amount of this sudscontrolling agent that will sufficiently control the suds to result in alow-sudsing laundry detergent for use in automatic laundry washingmachines.

The compositions herein will generally comprise from 0% to about 5% ofsuds suppressor. When utilized as suds suppressors, monocarboxylic fattyacids, and salts therein, will be present typically in amounts up toabout 5%, by weight, of the detergent composition. Preferably, fromabout 0.5% to about 3% of fatty monocarboxylate suds suppressor isutilized. Silicone suds suppressors are typically utilized in amounts upto about 2.0%, by weight, of the detergent composition, although higheramounts may be used. This upper limit is practical in nature, dueprimarily to concern with keeping costs minimized and effectiveness oflower amounts for effectively controlling sudsing. Preferably from about0.01% to about 1% of silicone suds suppressor is used, more preferablyfrom about 0.25% to about 0.5%. As used herein, these weight percentagevalues include any silica that may be utilized in combination withpolyorganosiloxane, as well as any adjunct materials that may beutilized. Monostearyl phosphate suds suppressors are generally utilizedin amounts ranging from about 0.1% to about 2%, by weight, of thecomposition. Hydrocarbon suds suppressors are typically utilized inamounts ranging from about 0.01% to about 5.0%, although higher levelscan be used. The alcohol suds suppressors are typically used at 0.2%-3%by weight of the finished compositions.

Fabric Softeners--Various through-the-wash fabric softeners, especiallythe impalpable smectite clays of U.S. Pat. No. 4,062,647, Storm andNirschl, issued Dec. 13, 1977, as well as other softener clays known inthe art, can optionally be used typically at levels of from about 0.5%to about 10% by weight in the present compositions to provide fabricsoftener benefits concurrently with fabric cleaning. Clay softeners canbe used in combination with amine and cationic softeners as disclosed,for example, in U.S. Pat. No. 4,375,416, Crisp et al, March 1, 1983 andU.S. Pat. No. 4,291,071, Harris et al, issued Sept. 22, 1981.

Other Ingredients--A wide variety of other ingredients useful indetergent compositions can be included in the compositions herein,including other active ingredients, carriers, hydrotropes, processingaids, dyes or pigments, solvents for liquid formulations, solid fillersfor bar compositions, etc. If high sudsing is desired, suds boosterssuch as the C₁₀ -C₁₆ alkanolamides can be incorporated into thecompositions, typically at 1%-10% levels. The C₁₀ -C₁₄ monoethanol anddiethanol amides illustrate a typical class of such suds boosters. Useof such suds boosters with high sudsing adjunct surfactants such as theamine oxides, betaines and sultaines noted above is also advantageous.If desired, soluble magnesium salts such as MgCl₂, MgSO₄, and the like,can be added at levels of, typically, 0.1%-2%, to provide additionalsuds and to enhance grease removal performance.

Various detersive ingredients employed in the present compositionsoptionally can be further stabilized by absorbing said ingredients ontoa porous hydrophobic substrate, then coating said substrate with ahydrophobic coating. Preferably, the detersive ingredient is admixedwith a surfactant before being absorbed into the porous substrate. Inuse, the detersive ingredient is released from the substrate into theaqueous washing liquor, where it performs its intended detersivefunction.

To illustrate this technique in more detail, a porous hydrophobic silica(trademark SIPERNAT D 10, DeGussa) is admixed with a proteolytic enzymesolution containing 3%-5% of C₁₃₋₁₅ ethoxylated alcohol (EO 7) nonionicsurfactant. Typically, the enzyme/surfactant solution is 2.5 × theweight of silica. The resulting powder is dispersed with stirring insilicone oil (various silicone oil viscosities in the range of500-12,500 can be used). The resulting silicone oil dispersion isemulsified or otherwise added to the final detergent matrix. By thismeans, ingredients such as the aforementioned enzymes, bleaches, bleachactivators, bleach catalysts, photo activators, dyes, fluorescers,fabric conditioners and hydrolyzable surfactants can be "protected" foruse in detergents, including liquid laundry detergent compositions.

Liquid detergent compositions can contain water and other solvents ascarriers. Low molecular weight primary or secondary alcohols exemplifiedby methanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols are preferred for solubilizing surfactant, but polyols such asthose containing from 2 to about 6 carbon atoms and from 2 to about 6hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and1,2-propanediol) can also be used. The compositions may contain from 5%to 90%, typically 10% to 50% of such carriers.

The detergent compositions herein will preferably be formulated suchthat, during use in aqueous cleaning operations, the wash water willhave a pH of between about 6.5 and about 11, preferably between about7.5 and 10.5. Liquid dishwashing product formulations preferably have apH between about 6.8 and about 9.0. Laundry products are typically at pH9-11. Techniques for controlling pH at recommended usage levels includethe use of buffers, alkalis, acids, etc., and are well known to thoseskilled in the art.

In order to make the present invention more readily understood,reference is made to the following examples, which are intended to beillustrative only and not intended to be limiting in scope.

EXAMPLE I

This Example illustrates several perfume formulations (A-C) made inaccordance with the invention for incorporation intocellulase-containing detergent compositions. The various ingredients andlevels are set forth in Table I below.

                  TABLE I                                                         ______________________________________                                                           (% Weight)                                                 Perfume Ingredient   A       B       C                                        ______________________________________                                        Hexyl cinnamic aldehyde                                                                            10.0    --      5.0                                      2-methyl-3-(para-tert-butylphenyl)-                                                                5.0     5.0     --                                       propionaldehyde                                                               7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-                                                        5.0     10.0    10.0                                     tetramethyl naphthalene                                                       Benzyl salicylate    5.0     --      --                                       7-acetyl-1,1,3,4,4,6-hexamethyltetralin                                                            10.0    5.0     10.0                                     Para-(tert-butyl) cyclohexyl acetate                                                               5.0     5.0     --                                       Methyl dihydro jasmonate                                                                           --      5.0     --                                       Beta-napthol methyl ether                                                                          --      0.5     --                                       Methyl beta-naphthyl ketone                                                                        --      0.5     --                                       2-methyl-2-(para-iso-propylphenyl)-                                                                --      2.0     --                                       propionaldehyde                                                               1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-                                                                 --      9.5     --                                       hexamethyl-cyclopenta-gamma-2-                                                benzopyrane                                                                   Dodecahydro-3a,6,6,9a-tetramethyl-                                                                 --      --      0.1                                      naphtho[2,1b]furan                                                            Anisaldehyde         --      --      0.5                                      Coumarin             --      --      5.0                                      Cedrol               --      --      0.5                                      Vanillin             --      --      5.0                                      Cyclopentadecanolide 3.0     --      10.0                                     Tricyclodecenyl acetate                                                                            --      --      2.0                                      Labdanum resin       --      --      2.0                                      Tricyclodecenyl propionate                                                                         --      --      2.0                                      Phenyl ethyl alcohol 20.0    10.0    27.9                                     Terpineol            10.0    5.0     --                                       Linalool             10.0    10.0    5.0                                      Linalyl acetate      5.0     --      5.0                                      Geraniol             5.0     --      --                                       Nerol                --      5.0     --                                       2-(1,1-dimethylethyl)-cyclohexanol                                                                 5.0     --      --                                       acetate                                                                       Orange oil, cold pressed                                                                           --      5.0     --                                       Benzyl acetate       2.0     2.0     --                                       Orange terpenes      --      10.0    --                                       Eugenol              --      1.0     --                                       Diethylphthalate     --      9.5     --                                       Lemon oil, cold pressed                                                                            --      --      10.0                                     Total                100.0   100.0   100.0                                    ______________________________________                                    

EXAMPLE II

This Example illustrates heavy duty granular detergents containingcellulase and the perfume formulations described in Example I. Theingredients in the typical granular detergents exemplified herein areset forth in Table II below.

                  TABLE II                                                        ______________________________________                                                           (% weight)                                                 Base Formula         1       2       3                                        ______________________________________                                        C.sub.12-13 linear alkylbenzene sulfonate                                                          9.0     9.0     9.0                                      (Na)                                                                          C.sub.14-15 alkyl ethoxy (EO = 0.6) sulfate                                                        1.6     1.6     1.6                                      (Na)                                                                          C.sub.12-18 alkyl sulfate                                                                          5.7     5.7     5.7                                      Polyacrylate (MW = 4500)                                                                           3.2     3.2     3.2                                      Aluminosilicate      26.3    26.3    26.3                                     Sodium silicate      0.6     0.6     0.6                                      Sodium carbonate     27.9    27.9    27.9                                     Sodium sulfate       8.9     8.9     8.9                                      Optical Brightener   0.2     0.2     0.2                                      Polyethylene glycol (MW = 4000)                                                                    1.7     1.7     1.7                                      Admix                                                                         Perborate            1.0     1.0     1.0                                      Cellulase.sup.1 (5 CEVU/g)                                                                         0.6     0.6     0.6                                      Protease.sup.2 (.0062 AU/g)                                                                        0.3     0.3     0.3                                      Lipase.sup.3 (206 LU/l)                                                                            0.2     0.2     0.2                                      Nonionic             3.0     3.0     3.0                                      Spray-on                                                                      Perfume A            0.4     --      --                                       Perfume B            --      0.4     --                                       Perfume C            --      --      0.4                                      Misc. (water and other minors)                                                                     9.4     9.4     9.4                                                           100.0   100.0   100.0                                    ______________________________________                                         .sup.1 CAREZYME ® commercially sold by NOVO Industries A/S.               .sup.2 Protease enzyme made by Genenecor International Inc. according to      Caldwell et al, U.S. Pat. No. 5,185,258.                                      .sup.3 LIPOLASE ® commercially sold by NOVO Industries A/S.          

The base formula illustrated herein can be made via a variety of knownprocesses including conventional spray drying techniques oragglomeration in apparatus such as powder mixers and fluid bedscommercially available from Lldige and Aeromatic, respectively.Agglomeration is especially suitable for preparing modern compactgranular detergents and entails initially forming a surfactant pasteusing standard mixers, after which the paste is agglomerated intoagglomerates and dried. Such processing techniques are well known in theart. The enzymes such as cellulase are dry mixed into the base formulaand the perfumes used herein are subsequently sprayed onto the baseformula so as to form the final granular detergent compositionsexemplified herein.

EXAMPLE III

This Example illustrates liquid laundry detergent compositionscontaining cellulase and the perfumes described in Example I. Table IIIillustrates the various ingredients of the liquid laundry detergent.

                  TABLE III                                                       ______________________________________                                                           (% weight)                                                 Component            4       5       6                                        ______________________________________                                        C.sub.14-15 alkyl ethoxy (EO = 2.25) sulfate                                                       18.0    18.0    18.0                                     N--Methyl N-1-Deoxyglucityl                                                                        5.0     5.0     5.0                                      cocoamide                                                                     Nonionic.sup.1       2.0     2.0     2.0                                      Citric Acid          3.0     3.0     3.0                                      Oleic acid           2.0     2.0     2.0                                      Ethanol              3.2     3.2     3.2                                      Boric acid           3.5     3.5     3.5                                      Monoethanolamine     1.1     1.1     1.1                                      1,2 Propanediol      8.0     8.0     8.0                                      Sodium cumene sulfate                                                                              3.0     3.0     3.0                                      Sodium hydroxide     3.8     3.8     3.8                                      Polyacrylate         1.2     1.2     1.2                                      Protease.sup.2 (.0145 AU/g)                                                                        0.3     0.3     0.3                                      Lipase.sup.3 (200 LU/l)                                                                            0.3     0.3     0.3                                      Cellulase.sup.4 (7.5 CEVU)                                                                         0.3     0.3     0.3                                      Perfume A            0.3     --      --                                       Perfume B            --      0.3     --                                       Perfume C            --      --      0.3                                      Misc. (water, brighteners, etc.)                                                                   45.0    45.0    45.0                                                          100.0   100.0   100.0                                    ______________________________________                                         .sup.1 Neodol 239 commercially available from Shell Oil Company               .sup.2 Protease enzyme made by Genencor International, Inc. according to      Caldwell et al, U.S. Pat. No. 5,185,258.                                      .sup.3 LIPOLASE ® commercially available from NOVO Industries A/S         .sup.4 CAREZYME ® commercially available from NOVO Industries A/S    

EXAMPLE IV

This Example illustrates laundry bars containing cellulase and a perfumein accordance with the invention. The laundry bars exemplified hereinare prepared by standard extrusion processes so as to be suitable forhandwashing soiled fabrics. Table IV sets forth the various ingredientsin the laundry bars.

                  TABLE IV                                                        ______________________________________                                                           (% weight)                                                 Component            7       8       9                                        ______________________________________                                        C.sub.12-13 linear alkylbenzene sulfonate                                                          10.0    10.0    10.0                                     (Na)                                                                          C.sub.14-15 alkyl sulfate (Na)                                                                     6.0     6.0     6.0                                      C.sub.14-15 alkyl ethoxy (EO = 0.6) sulfate                                                        3.0     3.0     3.0                                      (Na)                                                                          Sodium tripolyphosphate                                                                            7.0     7.0     7.0                                      Sodium pyrophosphate 7.0     7.0     7.0                                      Sodium carbonate     25.0    25.0    25.0                                     Aluminosilicate      5.0     5.0     5.0                                      Carboxymethyl cellulose                                                                            0.2     0.2     0.2                                      Polyacrylate (MW = 1400)                                                                           0.2     0.2     0.2                                      Brightener           0.2     0.2     0.2                                      Protease.sup.1       0.3     0.3     0.3                                      Cellulase.sup.2      0.3     0.3     0.3                                      Lipase.sup.3         0.3     0.3     0.3                                      Perfume A            0.4     --      --                                       Perfume B            --      0.4     --                                       Perfume C            --      --      0.4                                      Misc. (water, fillers and other minors)                                                            35.1    35.1    35.1                                                          100.0   100.0   100.0                                    ______________________________________                                         .sup.1 Protease enzyme made by Genencor International, Inc. according to      Caldwell et al, U.S. Pat. No. 5,105,258.                                      .sup.2 CAREZYME ®  commercially sold by NOVO Industries A/S               .sup.3 LIPOLASE ® commercially sold by NOVO Industries A/S           

Having thus described the invention in detail, it will be clear to thoseskilled in the art that various changes may be made without departingfrom the scope of the invention and the invention is not to beconsidered limited to what is described in the specification.

What is claimed is:
 1. A detergent composition comprising:(a) a cellulase enzyme; and (b) a perfume containing at least 25% by weight of at least one fragrance material selected from the group consisting of aliphatic ketones with a molecular weight of between 200 and 350 AMU, aromatic ketones with a molecular weight of between 150 and 350 AMU, aliphatic aldehydes with a molecular weight of between 160 and 350 AMU, aromatic aldehydes with a molecular weight of between 150 and 350 AMU, condensation products of aldehydes and amines with a molecular weight between 190 and 350 AMU, aromatic and aliphatic lactones with a molecular weight between 140 and 350 AMU, aromatic and aliphatic ethers with a molecular weight between 150 and 350 AMU, aliphatic alcohols with a molecular weight between 200 and 350 AMU, aromatic and aliphatic esters with a molecular weight between 190 and 350 AMU and mixtures thereof;wherein said perfume is substantially free of halogenated fragrance materials and nitromusks.
 2. The detergent composition of claim 1 wherein said enzyme is a fungal cellulase.
 3. The detergent composition of claim 1 further comprising from about 1% to about 55% of a surfactant.
 4. The detergent composition of claim 3 wherein said surfactant is selected from the group consisting of alkyl benzene sulfonates, alkyl ester sulfonates, alkyl ethoxylates, alkyl phenol alkoxylates, alkylpolyglucosides, alkyl sulfates, alkyl ethoxy sulfate, secondary alkyl sulfates and mixtures thereof.
 5. The detergent composition of claim 1 further comprising at least about 1% by weight of a detergency builder.
 6. The detergent composition of claim 1 wherein said perfume is present in an amount from about 0.001% to about 5% by weight of said composition.
 7. The detergent composition of claim 1 further comprising adjunct ingredients selected from the group consisting of bleaches, bleach activators, suds suppressors, enzyme stabilizers, polymeric dispersing agents, dye transfer inhibitors, soil release agents and mixtures thereof.
 8. The detergent composition of claim 1 wherein said composition is in the form of agglomerates and the density of said detergent composition is at least about 650 g/l.
 9. The detergent composition of claim 1 further comprising a polyhydroxy fatty acid amide for use as a surfactant.
 10. A detergent composition according to claim 1 wherein said composition is in the form of a laundry bar.
 11. A detergent composition according to claim 1 wherein said composition is in the form of a liquid.
 12. A method of laundering fabrics comprising the step of contacting said fabrics with an aqueous medium containing an effective amount of a detergent composition according to claim
 1. 